Buchwald-Hartwig Amination and C-S/S-H Metathesis of Aryl Sulfides by Selective C-S Cleavage Mediated by Air- and Moisture-Stable [Pd(NHC)(μ-Cl)Cl]2 Precatalysts: Unified Mechanism for Activation of Inert C-S Bonds

Shiyi Yang; Xiang Yu; Albert Poater; Luigi Cavallo; Catherine S J Cazin; Steven P Nolan; Michal Szostak

doi:10.1021/acs.orglett.2c03717

Buchwald-Hartwig Amination and C-S/S-H Metathesis of Aryl Sulfides by Selective C-S Cleavage Mediated by Air- and Moisture-Stable [Pd(NHC)(μ-Cl)Cl]₂ Precatalysts: Unified Mechanism for Activation of Inert C-S Bonds

Org Lett. 2022 Dec 23;24(50):9210-9215. doi: 10.1021/acs.orglett.2c03717. Epub 2022 Dec 8.

Authors

Shiyi Yang¹, Xiang Yu¹, Albert Poater², Luigi Cavallo³, Catherine S J Cazin⁴, Steven P Nolan⁴, Michal Szostak¹

Affiliations

¹ Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States.
² Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/Maria Aurèlia Capmany 69, Campus Montilivi, 17003 Girona, Catalonia, Spain.
³ KAUST Catalysis Center (KCC), King Abdullah University of Science & Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
⁴ Department of Chemistry and Center for Sustainable Chemistry, Ghent University, Krijgslaan 281, S-3, B-9000 Ghent, Belgium.

PMID: 36480689
DOI: 10.1021/acs.orglett.2c03717

Abstract

We report a combined experimental and mechanistic study on the Buchwald-Hartwig amination and C-S/S-H metathesis of aryl sulfides by selective activation of C-S bonds mediated by well-defined, air- and moisture-stable Pd(II)-NHC precatalysts, [Pd(NHC)(μ-Cl)Cl]₂. This class of Pd(II)-NHC precatalysts displays excellent activity in the cross coupling of aryl sulfides. Most crucially, we unravel the unified mechanism for activation of C-S bonds in the C-N cross-coupling and C-S metathesis manifolds, where the inert C-S bond serves as a precursor to valuable amine or thioether products.